Dyes of the 1, 4-diamino-2, 3-anthraquinone-dicarboximide series



the formation of a possibly substituted 5- or 6membered DYES OF THE 1,4-DIAM]NO-2,3-ANTHIRAQUI- NONE-DICARBOXINIDE SERIES Fritz Baumann, Leverkusen-Bayerwerk, Germany, as- 1 signor to Farbenfabriken Bayer Aktiengesellschaft, 0 NB! 0 NHI 3,0 Leverkusen, Germany, a corporation of Germany Rh Rpalkyl or and RFalkyl No Drawing. Filed Mar. 4, 1958, Ser. No. 718,980 9 The manufacture of these isoindolenines can be carried out by the process described in Angewandte Clams pmmty apphcaflon Germany 1957 Chemie, vol. 68 (1956), page 134 ff. It is moreover 11 Claims. (Cl,260--272) possible to use the process described in German patent specification No. 950,949 by which dicyananthraquinones 19 are hydrolysed with acids.

This invention relates to novel anthraquinone. dye- Amines f the general for ula stufis and to a process for their production. N

It has been found that anthraquinone dyestuffs are ob- 7 tainable by reacting o-dicyananthraquinones which may q be further substituted in'the anthraquinone radical, or 20 X iso'indolenines obtainable from ,these .o-dicyananthraquinones by treatment with acids or by reaction with alcoholates, alkali metal hydroxides, alkali metal sulphides, ammonia or ammonium derivatives, with amines of the general formula c which are suitable forthe new process are for example Z-aminoimidazoles, Z-aminothiazoles, 2-aminopyridines, 3-amino-1,2,4-triazoles, diaminopyrimidines, 'diaminotriazines and the like.

v The manufacture of the new anthraquinone dyestuffs V may be effected in a sirnplemanner by mixing the reg action components and heating the reaction mixture for some time. Temperatures within the range of 70230 C.,

: X I 'preferably140-210 C., are generally sufiicient. In some cases it may be expedient to work in the presence of an inert solvent'such as trichlorobenzene, nitrobenzene, o-dichlorobenzene or naphthalene. Dependent on the quantity of the amine of the above mentioned general Formula I employed and the iso'indolenines used, this amine wherein X stands for a carbon atom o'r a hetero atom such as N, O, or S, and Y for the radical required for ring. o-Dicyananthraquinones suitable for the process of the invention are for example LZ-dicyananthraquindne, 2,3-dicyananthraquinone or substituted o-dicyananthraquinones containing for example, halogen, nitro, amino, acylamino, hydroxyl, alkoxy groups or sulphonamide groups which. may be substituted at the nitrogen atom. 40 Compounds of this type are for example 1,4-diamino-2,3- dicyananthraquinone, 1,4-diamino-2,3 dicyano-6-chloranthraquinone, 1,4 diamino-2,3-dicyan-6,7-dichlor-anthraquinone, 1,4 diamin-2,3-dicyano-5-nitro-anthraquinone, 1,4 diamino'-2,3-dicyano-6-sulphodimethylamido-anthraquinone etc.

The isoindolenines which may also be used asa starting material and are obtainable from the aforesaid o-dicyananthraquinones by treatment with acids or by reactionvvith alcoholates, alkali metal hydroxides,. alkali metal sulphides 'or ammonia derivatives such as primary or secondary amines may be illustrated, when starting from 1,4-diamino-2,3-dicyananthraquinone, in one of their tautomeric forms bythe following formulae:

cule. It is therefore also possible for two difierent amine molecules to enter into one anthraquinone molecule. In this case 1 mol of the dicyananthraquinone' is,' for example, first reacted with 1 mol of one amine and then, either after previous isolation of the reaction product thus formed or directly in the same melt .with 1 mol of a second amine. The working up of the reaction product may be effected in usualmanner.

soluble in organic solvents and maybe used as pigments, forexample inpigrnent printing, or also as vat dyestuffs.

blue to green vats. In a mixture of pyridine and meth by known methods. V

' The following examples are given for the purpose of illustrating the invention 'Exam'le1-" NE: fi p r quinone and 18 parts by weight of 2-aminos6-ethoxy- NH benzthiazol are heated together to 160-170 C. for about 6 hours. The olive-green melt is then cooled to 120 C., 40 parts by weight ofpyridin'e are added with stirring NH, g and then, at 3040 C. 60 parts by-weight of acetone.

' The brownish black needles are filtered off at room temperature and the residue isthoroughly washed with ace- 0 NH: n tone. The dyestufi thus obtained in very good yield is H l C. barely soluble in organic solvents. When vatting in the presence of a little pyridine, an emeraldegreen vat is ob- NH tained. From the green vat cotton is dyed in greenish grey shades. i V f The 'dyes'tuif dissolves in concentrated sulphuric acid NH: 5 with a reddish brown colour; when pouring the sulphuric Patented July 19,

may enter once or twiceinto the anthraquinone 113016.

The new anthraquinone dyestuifs are generally barely a They generally yield very clearly and intensely coloured.

If desired, the dyestuifs thus obtained may be a lkylated' 3 parts by weight of 1,4-diarnino-2,3-dicyananthra V Example 2 parts by weight of 1,4-diamino-2,3-dicyananthraquinone are heated in the tenfold amount of 2-aminopyridine to the boil (204-206 C.) for 1 /2 to 2 hours. The'barely soluble nitrile thereby dissolves first with a blue colour. The melt becomes rapidly greener and already after hour long bluish black prisms separate out in the hot. On further heating the melt thickens. The reaction is now interrupted, the mixture cooled to 130-140 C., and 50 parts by weight of pyridine are carefully run into it. The crystals are filtered off with suction at 70 C., washed with pyridine and methanol and dried. The basic dystulf dissolves in concentrated hydrochloric acidwith a red colour, the acid paste shows a green colour and changes to bluish green on the addition of ammonia. The colour of the solution in concentrated sulphuric acid is olivish yellow-green. After suitable formulation, the substance may be used in pigment printing.

Example 3 0 1TH: R

6 parts by weight of Z-amino-benzimidazol and 300 parts by weight of trichlorobenzene are heated at 200 C. for several hours. Whilst the reaction product partially precipitates, the mixture becomes dull green. After completion of the reaction, 200 parts by weight of acetone are carefully run into the mixture at about 50 C. and the product is filtered off with suction in the cold. The filter residue is washed with acetone and dried. The new dyestufi dissolves in sulphuric acid with a yellowish brown colour, yields in a mixture of pyridine and methanol with the addition of sodium hydroxide solution a blue sodium salt, vats cornflower blue and dyes cotton from the vat olive green. It may be recrystallized from quinoline wherein it dissolves with a clear green colour. The substance may very easily be alkylated in a mixture of pyridine and methanol for example by using dimethylsulfate or diethylsulfate. The alkylated derivative also yields olive greendyeings which however show no longer the sensitivity to alkali of the starting material.

Example 4 =10 parts by weight of 1,4-'diamino-2,3-dicyananthraquinone, 10 parts by weight of Z-amino-benzimidazol and 300 parts by weightof trichlorobenzene are heated under reflux to about 200 C(for 1 hour and then to 215-2l8 C. for 4-5 hours. After. /z hour the initially blue melt has already acquired an olive green colour. With the splitting off of ammonia the crystallized condensation product precipitates. tion has only a weak greyish blue colour. The barely soluble dyestuff thus formed may be filtered off with suction on a suction filter either'directly or after previous dilution with a suitable'solvent such as methanol, acetone, pyridine. After washing with methanol and drying, a black crystal powder is obtained. The substance dissolves in concentrated sulphuric acid with an orange-brown, in sulphuric acid (60 B.) with a red At the end,*the solu-' colour. The vat colour is blue. The dyestulf which is barely soluble in organic solvents dyes vegetable fibres from the vat in full greenish grey shades and may also be used for printing. The imidazole derivative thus obtained may be alkylated in usual manner, for example by the following process:

A mixture of- 4 parts by weight of the imidazole dyestuff described 7 above a 5 parts by weight of potash 6 parts by weight of p-toluene-sulphonic acid methylester and I 40 parts by weight of nitrobenzene is heated with stirring to C. for about /2 hour. The methylated dyestuff is filtered off with suction at room temperature, washed with nitrobenzene, methanol and, finally, with water, in order to remove the salts. By this alkylation three methyl groups are introduced into the dyestufi molecule. Instead of the p-toluene-sulfonic acid methyl ester there can be used also the p-toluene sulfonic acid ethyl ester. In contrast to the starting substance, the alkyl derivatives no longer changes when suspended in a mixture of pyridine and methanol with sodium hydroxide solution. The color' of its solution in sulfuric acid is reddish brown, the vat color greenish blue. The dyestutf which crystallizes in fine black prisms dyes vegetable fibers from the vat in greyish black shades. The preparation of the dyestuff and the subsequent alkylation can be carried out also without separating the dyestuif before the alkylation.

A dyestuff which is very similar to the above obtained methylated dyestulf is obtained by reacting 45 parts by weight of Z-amino-l(N)-methyl-benzimidazol with 29 parts by weight of 1,4-diamino-2,3-dicyano-anthraquinone in the manner described above. Cotton is dyed with both dyestulfs from the vat in nearly equal shades, but the dyestuffs show minor differences in their properties if used in a printing process, for example they need a different time for their fixation.

Example 5 29 parts by weight of 1,4-diamino-2,3-dicyan-anthraquinone and 15 parts by weight of 2-amino-benzimidazole are caused to react with one another in 600 parts by weight of trichlorobenzene at -185 C., until the starting material disappears. After working up as usual, a crystalline black reaction product is obtained in good yield which. dissolves in boiling quinoline with a green color. The color of the solution in 96 percent sulfuric acid is brown; by flocculating the sulfuric acid solution in an acid medium a grey paste is obtained which changes to bluish grey in an ammoniacal medium. On slight heatin'g'with an alkaline sodium hydrosulfite solution the compound yields a blue vat.

The product may be further reacted with another mol of amino-benzimidazole or another amino compound. The dyestuffs obtained can be alkylated as described in Example 4.

Example 6 20 parts by weight of the product obtainable according to Example 5, paragraph 1, 10 parts by weight of 2-amino- 6-ethoxy-benzthiazole and 400 parts by weight of trichlorobenzene are heated together to the boil, until the splitting off of ammonia is completed. After being cooled off, the dyestuif is filtered off with suction, washed with trichlorobenzene and methanol and dried. In contrast to the starting material, the new compound vats readily and immediately with a bluish green color, dissolves with difficulty in boiling quinoline with an olive black color and is obtained therefrom in small black needles. The subscribed in Example 4.

7 In a boiling nitrobenzene bath, "3 parts by weight'of 1,4-diamino-2,3-dicyanoanthraquinone and 12 'parts' by' weight of 3-amino-1,2,4-triazole are melted together. Since the reaction mixture thickens as the reaction pro-' ceeds, another 6 parts byweight of 3-amino-l,2,4-triazol e are added. On further heating-a stage is again reached after about 2 hours 'in which further stirring is almost impossible. The melt is then cooled to 150 C., diluted with 50 parts by weight of dimethylformamide, briefly heated again to l60 C. another 25 parts by weight Qf'di methylformamide are added, and, finally, the pigment'dyestuflf is-filtered off with suction at 40 C. The filter residue is washed with dimethyl-formamide and methanol, until the discharge liquid is clear. By working up in this manner a pure product is immediately obtained which crystallizes in greyish black small needles. The vat color is blue, the solution in concentrated sulfuric acid olivish, green, the acidic paste is also olive green and changes to greyish green'on the addition of an excess of ammonia.

The dyestufE can be alkylated as described in Example 4. Example 8 2 parts by weight of 1,4-diamino-2,3-dicyanoanthraquinone, 4 parts by weight of 2-amino-4-methyl-pyrimidine and 40 parts by weight of trichlorobenzene are heated to the boil under reflux for8 hours.

due washed several times with methanol.

For purification the filter residue, still moist with methanol, is suspended with 120 parts by weight of a mixture of pyridineand methanol (1:1), treated with 1 part by weight of a 30 percent sodium hydroxide solution and briefly heated to 40 C. The product is then filtered off from the insoluble residue and the blue filtrate is diluted with about 800 parts by weight of water. iBluish green flakes thus precipitate which are collected on a filter, washed several times with water and, finally, dried.v

The substance vats blue and, on shaking the vat with air, yields an olivish green paste. The color of the solution in concentrated sulfuric acid is dull olivish green.

By directly melting 1,4-diamino-2,3-dicyananthraquinone with an excess of 2-amino-4-methyl-pyrimidine at 210 C. for 3. hours, a barely vattable product is obtained which dissolves in sulfuric acid with a blackish brown I 10 parts by weight of 1,4-dihydroxy-2,3-dicyanoanthra-' quinone, 50 parts by weight of 2-aminobenzimidazole' and 25 parts by weight of nitrobenzene areheated with stirring on a boiling o-dichlorobenzene bath. At 180 C. the

6 dyestuifs. The formation ofthedyestuff is expediently carried out in excess ,amine with the use of a little solvent as shown by the following composition: 25 parts by weight of quinone r 70 parts by weight of 2-amino-4,5 dimethylthiazole parts by weight of trichlorobenzene 1,4-diamino-2,3-dicyananthr-a- This mixture is heated to 180 C. for 1 /2 hours and at.

For some colouring eifects mixed dyestuffs have sometimes certain advantages. .Compounds of this kind are obtained for example in the following manner:

120 parts by weight of nitrobenzene 7.2 parts by weight of 1 ,4-diamino-2,3-dicyananthraquinone 4.5 parts by weight of 2-amino-5-chlorobenzimidazole are heated together to ISO-190 C. for about 2% hours andthen briefly to 200 C. 3.8 par-ts by weight of 2- :aminobenzimidazole are then added and the whole is p The product is" then filtered oif with suction at 40 C. and the filter resi stirred at 208 C. for another 5 hours. After isolation,

the mixed dyestuil is obtained in a yield of 13 parts by weight.

The sequence can also be altered and 2+aminobenzimidazole can first be added and Z-amino-S-chlorm benzimidazole can then be acted upon the former. Neither yield nor quality of the dyestuif are influenced'by it.

mixture melts together and the temperature rises to about 195 C. with a vigorous splitting 01f of ammonia. As soon as.the mass. has, thickened, a further 150 partsby weight of nitrobenaene are added and. the reaction ture is allowed to react for a further /2 hour; The cold;

blackish brown crystalline mass is diluted with acetone,

filteredoff and washed with acetone, until the discharge Example 11 58 parts; by weight 20f l,4-diamino-2,3-dicyananthraqui none; f q f i 28 parts by weight of 2 -aminobenzimida zole I 900Tparts. by weight of trichlorobenzene 42 parts by weight of the recrystallised intermediate 15 parts by W'eight'of 2-amino-1(N)-methyl-benzimidazole 400 parts by weight of trichlorobenzene is heated to the boil for 7 hours and, then worked up. Yield: 50 parts by weight of a mixed .dyestufl vatting, with a blue colour. The product dyes cotton a greyish black shade. I

The synthesis of other combinations is also possible, such as the preparation of. dyestuffs .ef the following general formula wherein the ring A and the ring B are difierent, R is a hydrogen atom or an alkyl group and wherein the anthraquinone radical may further be substituted e.g. in the 5 and/or 6 position by halogen, alkyl or al xyr urse i Example 12 7.2 parts by weight of 1,4-diamino-2,El-rlicyantl' raquinone 10 parts by weight of 2-amino-5(6)-chlorobenzimidazole 100 parts by weight of trichlorobenzene are kept boiling with stirring until the splitting oil of ammonia is completed and the dyestufi thus formed is worked up as described in Example 1.

By dissolution of the crude product in 96 percent sulphuric acid and dilution of this solution with 50 percent sulphuric acid below 20 C. there is formed a well crystalshades which turn greenish grey upon boiling with soap.

1,4-diarnino-5,8-dirncthxy 2,3 dicyananthraquinone' used as starting material can be prepared for example as follows:

HA3 0 3 NH:

H0 (H) ('31 H800 El) ('31 Toluene Cl sulphonic Cl Toluene -Cl Boracetic acid ester sulpharnide ester Cl Cl seponili- -Cl cation II II HO 0 l Etc 0 Cl H 0 NH:

(QOCCHQ:

B300 0 H300 c r n, moo o n,

HaCO O\ 3 Nalsol line sulphate. The vat dyeings produced with this dyestutr' distinguish themselves only little in their shade from the dyeings obtained by the'process of Example 4.

In a similiar manner, 2-amino-5,7-dichlorobenzimidazole can be used for the conversion. In this case there are obtained from 1 part by weight of 1,4-diarnino-2,3- dicyananthraquinone, 2 parts by weight of a vat dyestufr crystallising in greyish black needles.

Example 1 3 By condensation of 4 parts by weight of 1,4-diamino- 2,3-dicyananthraquinone with 6 parts by weight of 2 amino 5(6) methoxybenzimidazole in 60 "parts by weight of boiling trichlorobenzene there is also formed a bluish grey vat dyestufl with splitting ofi ammonia. The vat colour is greenish blue, the colour of the solution in concentrated sulphuric acid brownand in formicacid dull violet. The fastness to wet processing can be improved by subsequent alkylation.

Example 14 Intense grey vat dyestuffs are also obtainable by heat-.

Example 15 A mixture consisting of parts by weight of 1,4-diamino-5,8-dimethoxy-2,3-

dicyananthraquinone 27 parts by weight of 2-aminobenzirnidazole and 400 parts by weight of nitrobenzene is heated to 2oo 20s c. for about 7 am. After" are barely vattable.

, soluble in cold pyridin e. Thealkylation product dyes II J ' moo 0 H300 1,4-diamin0 5,8-dimeth0xy 2,3 dicyananthraquinone dissolves in 96 percent sulphuric acid with a green shade, and in concentrated hydrochloric acid with a reddish violet shade; the vat colour is also reddish violet.

Example 16 .When 3 parts by weight of 2,3-dicyananthraquinone are melted together with 18 parts by weight of Z-amino- 'benzthi azole at l70-l75 C. reaction takes place very rapidly and the composition becomes thick very soon. The temperature is kept for some time. The reaction product crystallising in brownish red needles can be worked up upondilution with a suitable organic solvent. The dyestuff obtained in this way dissolves. in concentrated sulphuric acid with a yellowish brown colour, vats with a green colour and dyes vegetable fibres in orange brown shades. When the dyestutf is alkylated with ;toluene sulphonic acid esters in the presence of potassium carbonate at C., the brown prisms of the starting material change into small orange yellow needles which Example 17 After heating 30 parts by weight of 2,3-dicyananthraquinone with 60 parts by weight of 2 aminobenzimidazole in 600 parts by weightof trichlorobenzene to 205'-210 C for Shouts :1 reaction product is obtained in very good yield after conventional working up the bulk of which consists apart from a few yellow leaflets of slightly yellow coloured needles. Upon heating in quinolinefor a short time the mixture changes quantitatively 'into 'u'nifor'm orange crystals. The orange compound which is stable in concentrated sulphuric acid to some extent is slightly split in 78 percent sulphuric acid. It yields a green vat and dyes cellulosev fibre a brown shade. Y

By alkylation with toluene sulphonic acid methyl ester the orange dyestufi changes into reddish brown prisms which, in contrast to the starting material, are no longer cotton from a vat in orange shades.

* Examplef18 p 10 parts "by. weight "of. Z-ahrinobenzimidazoleahd 1201; 1 parts ,by. weight-of nitrobenzene are .heatedto 180 C. i

for about 8 hours., he mixture iathenfilteredbfi at this temperature, washed with hot pyridine andfina'lly with alcohol and dried. Yield: 16.8 parts by weight of dyestufi. The dyestulf dissolving infformic acid with a green colour and in 78 percent sulphuric acidwit-h a bluish red colour dyes cotton from a blue vat in greenish grey shades.

The above mentioned methoxyimino imide can be produced by theaction of sodium methylate'upon 1,4- di-amino-2,3-dicyananthraquinone.

Into a solution of 30 grams of sodium in 2880 parts by weight of methanol there are added 288 parts by weight of 1,4-diamino-2,3-dicyananthraquinone and the reaction product is heated to the boil for 5 hours. The mixture is cooled, fitered off by suction and-the residue is washed with methanol until the discharge is slightly blue.

The blackish blue prisms dissolve in hydrochloric acid with a red colour, in formic acid with ,a dull greenish Into 420 millilitres of methanol, ammonia is introduced with cooling (using a mixture of ice and commonsalt), until the solution reaches a volume of 600 millilitres at 0 C. Upon the addition of 28.8 grams of 1,4- diaminoanthraquinone-Z,S-dinitrile, the melt is heated to 120 C. for 8 hours in an autoclave at a pressure of 26 atmospheres. The mixture is cooled, filtered off with suction and washed with methanol until free from ammonia. The bluish black microscopic prisms are airdried. Vat: bluish violet, solution in concentrated sulphuric acid: red, in formic acid: dull greenish blue.

20 parts by weight of the reaction product thus obtained, 120 parts by weight of 2-amino-6-ethoxybenzthiazole and 25 parts by weight of trichlorobenzene are carefully heated to 200 C. The conversion takes place with vigorous reaction, blackish grey crystals separating Example 2.9 g. of 1,4-diamino-anthraquinone-2,3-dinitri1e are heated in g. of 2aminobenz oxazole at 210 C. for 6 hours. The melt thus obtained is diluted with 75 ml.

1 needles dissolve in sulfuric acid with reddishhrown, and

in pyridine/methanol/soda lye with weak, dull violet coloration. The product is insoluble in hydrochloric acid and formic acid. It dryes cotton from a blue-green vat in every strong olive shades.

I claim: r l 1. An anthraquinone dyest'ufi corresponding to the formula 1 0 NH: l l H \NH 0 N- O D l 2. An anthraquinone dyestuff corresponding to the formula 0 NH: w n c 8 NH N 45 NH) 3. An anthraquinone dyestuff corresponding to the formula 4. An anthraquinone dyestufi corresponding to the formula N 0 NH n ".5

NH 0 N 0 NH:

- 11 5. An anthraquinone dyestulf corresponding tQ-the 11. An anthraquinone dyestuff of the formula formula o NH: fi

H 1; p v x \NR1 a O l-N-C l E H I g V 1 O NHZ N-Ra N 10 wherein X is a radical selected from the group consisting NH i K of H, C1, N0

i O N V i. v a I w 0H, NH O and CH' O;' R is a radical selected from thegroup consisting'of H and lower alkyl; and R and R are each a radical selected from the group consisting of bz-ethoxy- H benzthiazol'yl-Z; pyridinyl-Z; benzirnidazolyl-Z; 1(N)- mthyl-berizimidazolyl-Z; 1,2,4-triazolyl-2; methylpyrimi- 20 dihyl-Zi berizthiazolyP-Z; 4-phcny1thiazolyl-2; 4-rnethylthia zolyl-Z; 4,5-dimethylthiazolyl-2; bz-chlorobenzimid- 6. The methylation product of the dyestufi of claim 1. azoliylq?bz methoxy bgnzimidazole, and pz; 7. The methylation product of the dyestufi of claim 2. hy ation and ethy Products thereof 8. The methylation product of the dyestufi of claim 3- 5 Refer e Ci i the fil f this Patent A 9. The methylat-ion product of the dyestuff of claim 4. I UNITED STATES PATENTS 10. The methylation product of the dycstuff of claim 5. 2,753,356 Laucius July 3, 1956 

11. AN ANTHRAQUINONE DYESTUFF OF THE FORMULA 